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In previous work, our group discovered a phenomenon in which a mixed polymer-salt or mixed micellar aqueous two-phase system (ATPS) separates into its two constituent phases as it flows within paper. While these ATPSs worked well in their respective studies to concentrate the target biomarker and improve the sensitivity of the lateral-flow immunoassay, different ATPSs can be advantageous for new applications based on factors such as biomarker partitioning or biochemical compatibility between ATPS and sample components. However, since the mechanism of phase separation in porous media is not completely understood, introducing other ATPSs to paper is an unpredictable process that relies on trial and error experiments. This is especially true for polymer-polymer ATPSs in which the characteristics of the two phases appear quite similar. Therefore, our group aimed to develop semiquantitative guidelines for choosing ATPSs that can phase separate in paper. In this work, we evaluated the Washburn equation and its parameters as a potential mathematical framework to describe the flow behavior of polymer-salt and micellar ATPSs in fiberglass paper. We compared bulk phase fluid characteristics and identified the viscosity difference between the phases as a key determinant of the potential for phase separation in paper. We then used this parameter to predict the phase separation capabilities of polyethylene glycol (PEG)-dextran ATPSs in paper and control the composition of the leading and lagging phases. We also, for the first time, successfully demonstrated the phase separation phenomenon in hydrogels, thereby extending its application and potential benefits to an alternative porous medium.

Replacing synthetic polymers with renewable alternatives is a critical challenge for the packaging industry. This research investigated the use of leaf-based proteins as a sustainable co-binder in the coating formulations for paper-based packaging and other applications. Protein isolates from tobacco leaf and alfalfa concentrates were characterized using the Pierce protein assay, Kjeldahl nitrogen, and gel electrophoresis. The proteins were tested as co-binders in a typical latex-based paper coating formulation. The rheology and water retention properties of the wet coating and the surface, optical, structural, and strength properties of coated papers were measured. The coating performance was affected by the purity, solubility, and molecular weight of the tobacco protein and exhibited a shear-thinning behavior with lower water retention than soy protein. Analysis by scanning electron microscopy and time of flight secondary ion mass spectroscopy on the dried coating layer containing tobacco protein showed enhanced porosity (advantageous for package glueability) relative to the control latex coating. The tobacco protein offers adequate coverage and coating pigment distribution, indicating that this protein can be a suitable option in coatings for packaging applications.

RESUMEN: El diseño del aislamiento es uno de los aspectos más importantes del diseño del transformador, y de él depende en gran medida su calidad y fiabilidad. El aislamiento usado a lo largo de la historia está formado por materiales celulósicos, principalmente papel y cartón, y líquidos dieléctricos, especialmente aceite mineral, que rellenan las cavidades de estos materiales, proporcionando una mayor rigidez dieléctrica. Además, el líquido dieléctrico cumple las funciones de aislar las partes activas del transformador, transferir el calor de los conductores y diagnosticar el estado del equipo. Por estas razones, varios miles de millones de litros de aceite son utilizados en los transformadores de todo el mundo. Sin embargo, debido a la poca biodegradabilidad de los aceites minerales y el agotamiento de las reservas petrolíferas, se ha impulsado desde hace años una búsqueda de un nuevo líquido dieléctrico capaz de sustituir al aceite mineral y cumplir con las exigencias medioambientales. Los fluidos basados en ésteres, naturales y sintéticos, ofrecen varias ventajas comparados con los aceites minerales, como son su mayor biodegradabilidad y punto de inflamación, pero, sin embargo, su mayor viscosidad influye negativamente en los procesos de impregnación y de evacuación del calor. Por eso, es necesario el estudio del proceso de impregnación con líquidos dieléctricos basados en ésteres. El presente Trabajo de Fin de Grado consiste en una simulación computacional del proceso de impregnación de sólidos celulósicos usados en transformadores de potencia con líquidos dieléctricos. La fiabilidad del aislamiento depende en gran medida del proceso de impregnación, que garantiza que no queden cavidades en la celulosa y así evitar descargas parciales. Un paso importante previo a la realización de la simulación es la caracterización de los materiales a utilizar, sólidos celulósicos y aceites dieléctricos. Usando el software de dinámica de fluidos ANSYS Fluent en medios porosos, se pretende realizar una simulación del proceso de impregnación en varios materiales celulósicos (madera fenólica, cartón y pressboard) y con varios aceites dieléctricos (aceite mineral y éster natural) para obtener una primera aproximación del resultado del proceso sin tener que recurrir a métodos experimentales. ABSTRACT: The insulation design is one of the most important aspects of transformer design, and its quality and reliability depend to a large extent on it. The insulation used throughout history consists of cellulosic materials, mainly paper and cardboard, and dielectric liquids, especially mineral oil, which fill the cavities of these materials, providing greater dielectric strength. In addition, the dielectric liquid performs the functions of insulating the active parts of the transformer, transferring heat from the conductors and diagnosing the condition of the equipment. For these reasons, several billion liters of oil are used in transformers around the world. However, due to the poor biodegradability of mineral oils and the depletion of oil reserves, a search for a new dielectric fluid capable of replacing mineral oil and meeting environmental requirements has been underway for years. Ester-based fluids, both natural and synthetic, offer several advantages over mineral oils, such as higher biodegradability and flash point, but their higher viscosity, however, has a negative influence on the impregnation and heat dissipation processes. Therefore, it is necessary to study the impregnation process with ester-based dielectric liquids. This project consists of a computational simulation of the impregnation process of cellulosic solids used in power transformers with dielectric liquids. The reliability of the insulation depends to a large extent on the impregnation process, which ensures that no cavities are left in the cellulose and thus avoids partial discharges. An important step prior to the simulation is the characterization of the materials to be used, cellulosic solids and dielectric oils. Using the ANSYS Fluent fluid dynamics software in porous media, it is intended to perform a simulation of the impregnation process in various cellulosic materials (phenolic wood, cardboard and pressboard) and with various dielectric oils (mineral oil and natural ester) to obtain a first approximation of the result of the process without having to carry out experimental methods. Grado en Ingeniería en Tecnologías Industriales

Significance: Despite the importance of the cell membrane in regulation of drug activity, the influence of drug treatments on its physical properties is still poorly understood. The combination of fluorescence lifetime imaging microscopy (FLIM) with specific viscosity-sensitive fluorescent molecular rotors allows the quantification of membrane viscosity with high spatiotemporal resolution, down to the individual cell organelles. Aim: The aim of our work was to analyze microviscosity of the plasma membrane of living cancer cells during chemotherapy with cisplatin using FLIM and correlate the observed changes with lipid composition and cell’s response to treatment. Approach: FLIM together with viscosity-sensitive boron dipyrromethene-based fluorescent molecular rotor was used to map the fluidity of the cell’s membrane. Chemical analysis of membrane lipid composition was performed with time-of-flight secondary ion mass spectrometry (ToF-SIMS). Results: We detected a significant steady increase in membrane viscosity in viable cancer cells, both in cell monolayers and tumor spheroids, upon prolonged treatment with cisplatin, as well as in cisplatin-adapted cell line. ToF-SIMS revealed correlative changes in lipid profile of cisplatin-treated cells. Conclusions: These results suggest an involvement of membrane viscosity in the cell adaptation to the drug and in the acquisition of drug resistance.

Fibrinogen is a blood protein that is essential for clotting. It is converted into the polymer fibrin by the blood enzymes thrombin and factor XIIIa. Fibrinogen is one of the first proteins to be depleted in heavily bleeding patients. Patients with early hypofibrinogenemia need urgent fibrinogen replenishment to prevent the onset of haemorrhage and death. However, currently there is no rapid, sensitive, cheap and easy-to-use fibrinogen assay that can detect fibrinogen concentrations. In this study, we have developed a new paper-based diagnostic to quantify the fibrinogen concentration in blood at room temperature. This diagnostic is a 2-step process: first, plasma is added onto thrombin-treated paper strips where fibrinogen is converted to fibrin; then the strips are placed into an aqueous dye bath where elution occurs. The test operates by measuring the change in hydrophobicity, which increases with fibrinogen concentration under otherwise constant conditions. The diagnostic can precisely measure fibrinogen concentration within the range of 0-2 g L-1, which is ideal for the clinical diagnosis of hypofibrinogenemia. Furthermore, testing needs only 12 μL of plasma, 60 mU of thrombin and 7.5 minutes of testing. This diagnostic has the potential to revolutionise point of care testing and save many lives.

Hypotheses (1) The equilibrium size and characteristics of a radially wicked fluid on porous material such as paper is expected to be dependent on the fluid properties and therefore could serve as a diagnostic tool. (2) The change in wicked stain size between biological fluids is dependent on a change in solid-liquid surface interfacial energy due to protein adsorption. Experiments Sessile droplets of increasing volume of blood, its components, and model fluids were deposited onto paper and the equilibrium stain size after coming to a halt was recorded. The contact angle of fluid droplets on model cellulose surfaces was measured to quantify the effect that blood protein adsorption at the solid-liquid interface has on radially wicked equilibrium size. Finally the significance of droplet evaporation for the time scale of interest was analysed. Findings The final stain area of all fluids tested on paper scales remarkably linearly with droplet volume. Different fluids were compared and the gradient of this linear relation was measured. Model fluids varying in surface tension and viscosity all behave similarly and exhibit a constant gradient. Blood and its components produce smaller stains, demonstrated by lower gradients. The gradient is a function of protein concentration, thus the mechanism of this phenomenon was identified as protein adsorption at the cellulose-liquid interface. The slope of the area/volume relationship for droplets is an important quantitative mechanistic variable.

Electron beam irradiation (EBI) is an alternative treatment for intrinsic viscosity (IV) control in cellulose pulps, but has never been integrated in full bleaching sequences for comparison to conventional methods. Both eucalyptus kraft (EK) paper pulp and beech sulfite (BS) dissolving pulp were subjected to totally chlorine free (TCF) bleaching sequences comprising either EBI, ozone, or both for IV control. Additionally, effects of EBI on hexenuronic acid (HexA) and xylan were investigated. IV was adjusted to 450–500 mL g−1 and properties including carbonyl content, kappa, brightness, alkali-resistance and sugar composition were compared. Pulps produced with EBI had a higher alkali-resistance, uniformity and less cellulose oxidation. However, the degree of bleaching (DoB) was low without the use of ozone. HexA content in a birch pulp was halved by EBI. Isolated xylans were more resistant to irradiation than cellulose with little decrease of molar masses and moderate oxidation.

This work investigates the spreading dynamics of three candidate sol-gel solutions, of ranging viscosities, surface tensions and densities, and compares them with water and two commercial blood substitute products. Droplets were created with different sizes (10 to75μL) and impact velocities (1.4 to 6.0m/s) to strike 176gsm cardstock. Over 2200 droplets were created using the six different fluids and their final dried stain diameter was measured. Droplet spread was plotted using the Scheller and Bousfield correlation and uses effective viscosity as a parameter for non-Newtonian fluids. Comparing the results to an expected whole human blood range validated the spread of the candidate FBS sol-gel material in passive drip bloodstain pattern simulation. These findings complement the practical application of the material as a safe substitute for demonstrating droplet spread under controlled conditions on hard paper surfaces.

Comparative studies of the effects of two commercial enzyme formulations on fiber refining were conducted. Extensive basic characterisation of the enzymes involved, assessment of their hydrolytic activities on different model substrates as well as on different pulps (softwood sulfate, softwood sulfite, hardwood sulfate) were evaluated. Both enzyme formulations showed endoglucanase as well as some xylanase and β-glucosidase activity. In addition, Enzyme A reached a CMC end viscosity of 19.5 mPa compared to 11.1 mPa for Enzyme B. Reducing sugar release almost doubled from 695 μmol mL−1 for hardwood sulfate pulp to 1300 μmol mL−1 for softwood sulfite pulp with Enzyme B under the same conditions. Enzyme A increased the degree of refining even under non-ideal conditions from 23 °SR to up to 50 °SR. Further characterization of hand sheets, made from enzyme pre-treated and refined cellulose fibers with Enzyme A and B, showed that Enzyme A had the best effects leading to hand sheets with increased tensile strength and low air permeability. In summary, the increase in the degree of refining seen for Enzyme A correlated to higher xylanase and β-glucosidase activity and lower endoglucanase activity.

The production processes of the pulp and paper industry often run in campaigns, leading to large variations in the composition of wastewaters and waste sludges. During anaerobic digestion (AD) of these wastes, the viscosity or the production of extracellular polymeric substances (EPS) and soluble microbial products (SMP) may be affected, with the risk of foam formation, inefficient digester mixing or poor sludge dewaterability. The aim of this study was to investigate how viscosity and production of EPS and SMP during long-term AD of pulp and paper mill sludge is affected by changes in organic loading rate (OLR) and hydraulic retention time (HRT). Two mesophilic lab-scale continuous stirred tank reactors (CSTRs) were operated for 800 days (R1 and R2), initially digesting only fibre sludge, then co-digesting fibre sludge and activated sludge. The HRT was lowered, followed by an increase in the OLR. Reactor fluids were sampled once a month for rheological characterization and analysis of EPS and SMP. The production of the protein fraction of SMP was positively correlated to the OLR, implicating reduced effluent qualities at high OLR. EPS formation correlated with the magnesium content, and during sulphate deficiency, the production of EPS and SMP increased. At high levels of EPS and SMP, there was an increase in viscosity of the anaerobic sludges, and dewatering efficiency was reduced. In addition, increased viscosity and/or the production of EPS and SMP were important factors in sludge bulking and foam formation in the CSTRs. Sludge bulking was avoided by more frequent stirring. Electronic supplementary material The online version of this article (10.1007/s00449-019-02224-4) contains supplementary material, which is available to authorized users.

The current research intended to explore the hardwood pulps capabilities to produce cellulose (CNPs) and lignocellulose nanopapers (LNPs) and feasible enhancement of their performance for possible utilization in sustainable packaging. The high-yield hardwood pulps were then bleached to show the fundamental role of residual lignin on the ultrafine fibrillation processes, structural and barrier properties of nanopapers. X-ray diffraction results demonstrated that the crystallinity and crystallite size of CNPs and LNPs were lower than the corresponding starting pulps. Field emission scanning electron microscopy analysis showed that the average nanofibril diameter of the CNPs and LNPs are 35 nm and 23 nm, respectively. Elastic modulus of LNPs was found to be 9.1 and 10.8 GPa for Chemimechanical and Neutral sulfite semichemical pulps, respectively. The semi-porous and consolidated structure of LNPs prepared from CMP fibers contributed to yield the lowest water vapor transmission rate i.e. 108 g/m2.day which is promising for potential applications in packaging materials.

The aim of this work was to study the impact of shortening kraft pulping (KP) process integrated with extended oxygen delignification (OD) on the biorefinery process performance of eucalyptus. Data showed that using kraft pulps with high kappa number could improve the delignification efficiency of OD, reduce hexenuronic acid formation in kraft pulps. Pulp viscosity for a target kappa number of ∼10 was comparable to that obtained from conventional KP and OD process. The energy and alkali consumption in the integrated biorefinery process could be optimized when using a KP pulp with kappa number of ∼27. The process could minimize the overall methanol formation, but greater amounts of carbonate and oxalate were formed. The information from this study will be helpful to the future implementation of short-time KP integrated with extended OD process in actual pulp mill applications for biorefinery, aiming at further improvement in the biorefinery effectiveness of hardwood.

Quantitatively paper-based senor is performed with simple distance-readout on mixed cellulose ester (MCE) filter paper based on acetylcholinesterase (AChE)-mediated alginate hydrogel. The method is accomplished with the aid of the inhibition effect of target samples on the AChE enzyme-catalyzed hydrolysis of acetylcholine, which changes the pH value of the solution to release Ca2+ and trigger alginate hydrogelation. The viscosity of the solution is thus regulated with the presence of target samples in the reaction mixture, leading to a significant change in the diffusion diameter of the solution spotted on the filter paper. The concentration in the sample is quantitatively determined by ruler-measureable diffusion diameter of the spot on the paper. With successfully application for quantitatively sensing of organophosphorus pesticides (OPs), we show that the method exhibits excellent reproducibility with RSD (n = 5) as low as 0.09% and good selectivity for detection of OPs. The dynamic range of the method is up to 66.7 ng/mL with the limit-of-detection (LOD) of 3.3 ng/mL. The present study provides a new approach for developing paper-based sensors with quantitative distance-readout, by utilizing enzymatic inhibition to modulate liquid viscosity, which would be of value for target detection in complex samples.

Orientadores: José Vicente Hallak d'Angelo, Vinicius Bohrer Lobosco Gonzaga de Oliveira Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química Resumo: A polpação Kraft é o processo mais utilizado para extrair celulose para produção de papel, sendo crucial para suprir a demanda crescente por papel. A polpação gera (um subproduto chamado licor negro) um resíduo chamado licor negro. O licor é uma mistura de uma fração orgânica (lignina, polissacarídeos, entre outros) e uma fração inorgânica (principalmente íon contendo sódio e enxofre Na2SO4 e Na2CO3). O licor negro é regenerado na unidade de recuperação, e posteriormente da origem a um novo licor de cozimento. Geralmente a caldeira de recuperação é o maior gargalo deste processo, limitando a produção de celulose com base em sua capacidade de tratar licor negro. Uma alternativa para esse excesso é usar o licor em um processo para recuperar a lignina por meio de precipitação ácida, reduzindo a carga da caldeira, e aumentando a produção de celulose sem alterar a configuração do ciclo da recuperação química. A precipitação ácida da lignina foi estudada extensivamente, e ainda, uma grande parte dos estudos centraram-se em licores negros originados de coníferas e não angiospermas de clima tropical (por exemplo, Eucalyptus grandis) altamente difundida no Brasil. Como a madeira desempenha um papel vital na composição e nas propriedades físicas e químicas do fluido, estudos usando licores de coníferas não se aplicam a licores de madeira tropical. Considerando a importância da composição do licor ao estudar a recuperação da lignina, este estudo concentra-se em determinar a influência dos principais componentes do licor sobre suas propriedades físicas, visando um modelo preditivo para inferir a viscosidade do licor residual (filtrado) após a precipitação ácida da lignina, usando CO2, a partir de outras propriedades de fácil medição, como massa específica, e sólidos totais. Analisou-se as seguintes propriedades de licor: massa específica (25 °C - 80 °C), teor de sólidos totais, pH, viscosidade (25 °C-80 °C), e o impacto dos principais componentes dos licores. As amostras de processo foram coletadas em oito pontos diferentes do processo (lignina Kraft, licor negro diluído original; licor negro acidulado com pH 10,5, 10, 9,5, 9 e 8,5; e o primeiro filtrado da lignina Kraft em pH 8,5). Um método alternativo para medir a lignina Klason foi proposto e os resultados comparados com o do método padrão. Além de analisar os espectros FTIR, e também inferir insights a partir deles. Determinou-se também o coeficiente de extinção da lignina. Os resultados mostraram que o conteúdo inorgânico influencia mais a densidade do que os sólidos totais e a viscosidade, um resultado significativo, especialmente quando se lida com o aumento da concentração de carbonato devido ao uso de CO2. Diferentemente dos inorgânicos, a lignina, pode afetar mais os sólidos totais e a viscosidade. Os componentes inorgânicos e orgânicos afetam as propriedades físicas de forma diferente. Com base na caracterização física e química, e seu impacto na viscosidade, foi proposta uma correlação. A correlação produziu um modelo que explica o comportamento de viscosidade em diversos teores de lignina (140¿408 g/kg de sólidos secos), faixa de temperaturas (25 °C¿80 °C), sólidos totais (26 %¿32 %) e tensão de cisalhamento entre 0 s?1 ¿2000 s1 Abstract: Kraft pulping is the most widespread process used to extract pulp for paper production, being a crucial piece fulfilling the escalating demand for paper. The pulping process generates a waste stream called black liquor. Black liquor is a mixture of an organic fraction (lignin) and an inorganic fraction (primarily Na2SO4 and Na2CO3). Black liquor is recovered into a new cooking liquor in a recovery boiler. Currently, the recovery boiler is the major bottleneck of this process, limiting pulp production based on its capacity to treat black liquor. An alternative to process the excess of black liquor is to use part of this liquor in a process to recover lignin by means of an acid precipitation process, reducing boiler load while increasing pulp production without upgrading the chemical recovery cycle equipment. Lignin recovery by acid precipitation has been studied extensively, and yet, a large part of the studies have focused on black liquors originated from softwoods and not tropical- hardwoods (e.g., Eucalyptus grandis). Once the type of wood plays a vital role in the composition and consequently in the physical and chemical properties of black liquor, studies using softwoods liquors do not apply to tropical-hardwood liquors. Considering the importance of the liquor composition when studying the recovery of lignin. This study is focused not only in determining the influence of the main components of the liquor over its physical properties but also aims a predictive model to infer the viscosity of the residual liquor after lignin acid precipitation, using CO2, from readily measuring properties as density, total solids, and pH. The experiments were carried out by analyzing the following liquor properties: density (25 °C, 50 °C and 80 °C), total solids content, pH, viscosity (25°C, 50 °C and 80 °C), and measure the concentration and impact of the main components of the liquors. The process streams were collected in eight different locations (kraft lignin, original diluted black liquor; acidulated black liquor with pH 10.5, 10, 9.5, 9 and 8.5; and the first filtrate of kraft lignin at pH 8.5). An alternative method to determine Klason lignin was proposed and the results compared with the standard Klason method. Besides analyzing the FTIR spectra, and also drawing insights from it, the extinction coefficient for lignin was determined. The results have shown that the inorganic content influenced more the density than the total solids and viscosity, a significant result, especially when dealing with the rise in carbonate concentration due to the use of CO2. Unlike the inorganics, lignin affected the total solids and viscosity to more than two orders of magnitude. It was observed that inorganic and organic components affect physical properties differently. Based on the physical and chemical characterization, and their impact on viscosity, a correlation was proposed. The correlation yielded a model that explained the viscosity behavior in various lignin contents (140 ¿ 408 g/kg dry solids), temperatures range (25 °C ¿ 80 °C), solid contents (26 % ¿ 32 %) and shear stress between 0 s?1 ¿ 2000 s?1 Mestrado Engenharia Química Mestre em Engenharia Química

A modified process consisting of an initial mechanical refining (R) followed by a low-alkali (5.5% NaOH) cold caustic extraction (CCE) and finally an endoglucanase (EG) treatment (R-5.5%CCE-EG) was investigated for upgrading paper-grade pulp to dissolving pulp. Results showed that compared to the conventional process (9%CCE-EG), the modified process can decrease the alkali concentration (from 9% to 5.5%) to achieve a similar hemicelluloses removal while simultaneously enhancing the Fock reactivity (from 62.2% to 81.0%). The improved results were due to the fact that the mechanical refining resulted in favorable fiber morphological changes, including increased pore volume/size, water retention value and specific surface area. Consequently, the hemicelluloses removal was enhanced even under the subsequent low-alkali CCE condition. A synergic effect of refining, low alkali concentration and enzymatic activation was responsible for the higher reactivity of resulting dissolving pulp.

For enzymatic treatment of dissolving pulp, there is a need to improve the process to facilitate its commercialization. For this purpose, the high consistency cellulase treatment was conducted based on the hypothesis that a high cellulose concentration would favor the interactions of cellulase and cellulose, thus improves the cellulase efficiency while decreasing the water usage. The results showed that compared with a low consistency of 3%, the high consistency of 20% led to 24% increases of cellulase adsorption ratio. As a result, the viscosity decrease and Fock reactivity increase at consistency of 20% were enhanced from 510 mL/g and 70.3% to 471 mL/g and 77.6%, respectively, compared with low consistency of 3% at 24h. The results on other properties such as alpha cellulose, alkali solubility and molecular weight distribution also supported the conclusion that a high consistency of cellulase treatment was more effective than a low pulp consistency process.

Rationale : Saliva as a sample matrix is rapidly gaining interest for disease diagnosis and point-of-care assays because it is easy to collect (non-invasive) and contains many health-related biomarkers. However, saliva poses particular problems relative to more common urine and blood matrices, which includes low analyte concentrations, lack of understanding of biomolecule transportation and inherent viscosity variability in human samples. While several studies have sought to improve assay sensitivity, few have addressed sample viscosity specifically. The goal of this study is to minimize the effect of sample viscosity on paper-based analytical devices (PADs) for the measurement of pH and nitrite in human saliva. Methods : PADs were used to measure salivary pH from 5.0 to 10.0 with a universal indicator consisting of chlorophenol red, phenol red and phenolphthalein. Nitrite determination was performed using the Griess reaction. Artificial saliva with viscosity values between 1.54 and 5.10 mPa∙s was tested on the proposed PAD. To ensure the proposed PADs can be tailored for use in-field analysis, the devices were shipped to Australia and tested with human specimens. Results : Initial experiments showed that viscosity had a significant impact on the calibration curve for nitrite; however, a more consistent curve could be generated when buffer was added after the sample, irrespective of sample viscosity. The linear range for nitrite detection was 0.1 to 2.4 mg/dL using the improved method. The nitrite measurement in artificial saliva also showed a good correlation with the standard spectrophotometry method (p=0.8484, paired sample t-test, n=20). Measured pH values from samples with varying viscosities correlated well with the results from our pH meter. Conclusions : The inherent variation of salivary viscosity that impacts nitrite and pH results can be addressed using a simple washing step on the PAD without the need for complex procedures.

Growing interest in alternative and renewable energy sources has brought increasing attention to the integration of a pulp mill into a forest biorefinery, where other products could be produced in addition to pulp. To achieve this goal, hemicelluloses were extracted, either by steam explosion or by steam treatment, from Eucalyptus globulus wood prior to pulping. The effects of both pre-treatments in the subsequent kraft pulping and paper strength were evaluated. Results showed a similar degree of hemicelluloses extraction with both options (32-67% of pentosans), which increased with the severity of the conditions applied. Although both pre-treatments increased delignification during pulping, steam explosion was significantly better 12.9 kappa number vs 22.6 for similar steam unexploded pulps and 40.7 for control pulp. Finally, similar reductions in paper strength were found regardless of the type of treatment and conditions assayed, which is attributed to the increase of curled and kinked fibers. © 2013 Elsevier Ltd.

We have developed a photoacoustic (PA) sensor using a low-power, continuous- wave laser and a kHz-range microphone. The sensor is simple, flexible, cost-effective, and compatible with commercial optical microscopes. The sensor enables noncontact PA measurements through air, whereas most current existing PA techniques require an acoustic coupling liquid for detection. The PA sensor has three main components: one is the chamber that holds the sample, the second is a resonator column used to amplify the weak PA signals generated within the sample chamber, and the third is a microphone at the end of the resonator column to detect the amplified signals. The chamber size was designed to be 8 mm × 3 mm as the thermal diffusion length and viscous-thermal damping of air at room pressure and temperature are 2 and 1 mm, respectively. We numerically and experimentally examined the effect of the resonator column size on the frequency response of the PA sensor. The quality factor decreased significantly when the sample chamber size was reduced from 4 mm × 3 mm to 2 mm × 3 mm due to thermos-viscous damping of the air. The quality factor decreased by 27%, demonstrating the need for optimal design for the sample chamber and resonator column size. The system exhibited noise equivalent molecular sensitivity (NEM) per unit bandwidth (NEM / √ Δ f ) of ∼19,966 Hz − 1/2 or 33 × 10 − 21 mol or 33 zeptomol, which is an improvement of 2.2 times compared to the previous system design. This PA sensor has the potential for noncontact high-resolution PA imaging of materials without the need for coupling fluids.

Water soluble pullulan films were formatted into paper-based microfluidic devices, serving as a controlled time shutoff valve. The utility of the valve was demonstrated by a one-step, fully automatic implementation of a complex pesticide assay requiring timed, sequential exposure of an immobilized enzyme layer to separate liquid streams. Pullulan film dissolution and the capillary wicking of aqueous solutions through the device were measured and modeled providing valve design criteria. The films dissolve mainly by surface erosion, meaning the film thickness mainly controls the shutoff time. This method can also provide time-dependent sequential release of reagents without compromising the simplicity and low cost of paper-based devices.

Incorporation of nanofillers into a polymeric matrix has received much attention as a route to reinforced polymer nanocomposites. In the present work, an environmentally friendly chitosan (CTS)/titanium dioxide (TiO2) nanocomposite coating was designed/prepared and subsequently employed for imparting antibacterium and improved mechanical properties to cellulosic paper via surface coating. Effect of TiO2 nanoparticle loadings on the rheological behavior of nanocomposite coatings was investigated. Surface application of CTS/TiO2 nanocomposite coatings to cellulosic paper was performed, and the antibacterial activity and mechanical properties of surface-coated cellulosic paper were examined. Results showed that the increased TiO2 nanoparticle loadings decreased the viscosity and dynamic viscoelasticity of the as-prepared coatings, and improved the antibacterial activity and mechanical properties of surface-coated cellulosic paper. The optimum loading of TiO2 nanoparticles was identified at 10%. This work suggested that CTS/TiO2 nanocomposite coatings may have the potential to be used as a promising antibacterial protective coating for paper packaging.

We combined conventional inkjet printing technology with flexographic printing to fabricate drug delivery systems with accurate doses and tailored drug release. Riboflavin sodium phosphate (RSP) and propranolol hydrochloride (PH) were used as water-soluble model drugs. Three different paper substrates: A (uncoated woodfree paper), B (triple-coated inkjet paper) and C (double-coated sheet fed offset paper) were used as porous model carriers for drug delivery. Active pharmaceutical ingredient (API) containing solutions were printed onto 1 cm × 1 cm substrate areas using an inkjet printer. The printed APIs were coated with water insoluble polymeric films of different thickness using flexographic printing. All substrates were characterized with respect to wettability, surface roughness, air permeability, and cell toxicity. In addition, content uniformity and release profiles of the produced solid dosage forms before and after coating were studied. The substrates were nontoxic for the human cell line assayed. Substrate B was smoothest and least porous. The properties of substrates B and C were similar, whereas those of substrate A differed significantly from those of B, C. The release kinetics of both printed APIs was slowest from substrate B before and after coating with the water insoluble polymer film, following by substrate C, whereas substrate A showed the fastest release. The release rate decreased with increasing polymer coating film thickness. The printed solid dosage forms showed excellent content uniformity. So, combining the two printing technologies allowed fabricating controlled-release oral dosage forms that are challenging to produce using a single technique. The approach opens up new perspectives in the manufacture of flexible doses and tailored drug-delivery systems.

The lab-on-a-chip concept has led to several point-of-care (POC) diagnostic microfluidic platforms. However, few of these can process raw samples for molecular diagnosis and fewer yet are suited for use in a resource-limited setting without permanent electrical infrastructure. We present here a very low cost paper microfluidic device for POC extraction of bacterial DNA from raw viscous samples--a challenge for conventional microfluidic platforms. This is an example of "microfluidic origami" in that the system is activated by folding; demonstrated here is room temperature cell lysis and DNA extraction from pig mucin (simulating sputum) spiked with E. coli without the use of external power. The microfluidic origami device features dry reagent storage and rehydration of the lysis buffer. We demonstrate DNA extraction from samples with a bacterial load as low as 33 CFU ml(-1). Extraction times, starting from the raw sample, have been optimized to about 1.5 h without the use of external power, or to within 1 h using an oven or a heater block. The fabrication of this paper microfluidic device can be translated into high volume production in the developing world without the need for a semiconductor clean room or a microfabrication facility. The sample preparation can be performed with the addition of just the sample, water, ethanol and elute buffer to the device, thus reducing chemical hazards during transport and handling.

Two novel cellulase-poor xylanases from Coprinellus disseminatus SH-1 NTCC-1163 (enzyme-A) and SH-2 NTCC-1164 (enzyme-B) produced under solid-state fermentation mitigated kappa number of wheat straw soda-AQ pulps by 24.38 and 27.94% respectively after XE stages. The release of reducing sugars and chromophores was highest for both the enzymes at 10IU/g and reaction time 180min for 55°C at variable consistencies that is, 10% for enzyme-A and 5% for enzyme-B. (A)XECEHH and (B)XECEHH sequences improved brightness by 5.17 and 2.58% respectively at 4.5% chlorine charge. AOX in (A)XECEHH and (B)XECEHH sequences reduced by 56.11 and 55.75% respectively at 4.5% chlorine charge and 68.34 and 67.98% respectively at 2.25% chlorine charge respectively compared to control. Both the enzymes showed improvement in double fold and tear index with a decrease in burst and tensile index. SEM showed peeling, cracking and delamination in fibers due to enzyme treatment thus facilitating the penetration of bleach chemicals.

A sequence of treatments consisting of an initial xylanase treatment followed by cold alkaline extraction and a final endoglucanase treatment was investigated as a process for upgrading non-wood paper-grade pulps to dissolving-grade pulps for viscose production. Five commercial dried bleached non-wood soda/AQ paper pulps, from flax, hemp, sisal, abaca, and jute, were studied for this purpose. Commercial dried bleached eucalyptus dissolving pulp was used as reference sample. Sisal pulp showed the highest improvement in Fock's reactivity, reaching levels nearly as high or even higher than that of eucalyptus dissolving pulp (65%), and a low hemicellulose content (3-4%) when was subjected to this sequence of treatments. The viscosity, however, decreased considerably. A uniform and narrow molecular weight distribution was observed by size exclusion chromatography. (13)C nuclear magnetic resonance spectroscopy and Raman microspectroscopy revealed that the cellulose structure consisted of cellulose I.

The paper deals with the application of size exclusion chromatography (SEC) for the studies of paper degradation phenomena. The goal is to solve some of the technical problems connected with the calibration of multi-detector SEC system and to find the correlation between SEC and viscometric results of degree of polymerization of cellulose. The results gathered for the paper samples degraded by acidic air pollutant (NO(2)) are used as an example of SEC-MALLS application. From the correlation between intrinsic viscosities and absolute value of molecular masses obtained with SEC/MALLS (Multi Angle Laser Light Scattering) technique, Mark-Houwink coefficients for cellulose in cupri-ethylenediamine solution were determined. Thus obtained coefficients were used for the determination of viscometric degree of polymerization (molecular mass) of the aged samples. An excellent correlation was found between the chromatographic values of molecular masses obtained with SEC-UV/VIS detection and the viscometric ones utilizing the improved values of Mark-Houwink coefficients.

The feasibility of thermal ink jet printing as a robust process for biosurface engineering was demonstrated. The strategy investigated was to reconstruct a commercial printer and take advantage of its colour management interface. High printing resolution was achieved by formulating bio-inks of viscosity and surface tension similar to those of commercial inks. Protein and enzyme denaturation during thermal ink jet printing was shown to be insignificant. This is because the time spent by the biomolecules in the heating zone of the printer is negligible; in addition, the air and substrate of high heat capacity absorb any residual heat from the droplet. Gradients of trophic/tropic factors can serve as driving force for cell growth or migration for tissue regeneration. Concentration gradients of proteins were printed on scaffolds to show the capability of ink jet printing. The printed proteins did not desorb upon prolonged immersion in aqueous solutions, thus allowing printed scaffold to be used under in vitro and in vivo conditions. Our group portrait was ink jet printed with a protein on paper, illustrating that complex biopatterns can be printed on large area. Finally, patterns of enzymes were ink jet printed within the detection and reaction zones of a paper diagnostic.

In this work, depithed cardoon stalk (Cynara cardunculus) has been used with the objective of obtaining bleachable pulps. The material, once properly prepared, was subjected to one-step peroxyformic acid delignification. In order to study the process, a face-centred second order factorial design was developed which allowed the determination of the influences of four variables: concentrations of formic acid and hydrogen peroxide in the cooking liquor and the time and temperature of the treatment. Empirical mathematical models have been obtained which predict the yield, kappa index, residual lignin content, and viscosity of the pulps. These models demonstrate that in general the delignification was extensive, producing pulps with kappa indexes less than 25 in the majority of cases, with good yields in the range of 45-60%. However, the pulps seem to have been degraded in the reaction media, as can be deduced from the low viscosity values found: 260-520 mL/g.

The study was conducted to evaluate the quality of dissolving pulp of Musa sapientum L. (banana) plant stem and its potential for biorefinery. Introduction of pre-hydrolysis prior to any alkaline pulping process helps to reduce the content of hemicellulose and consequently produce acceptably high content of cellulose pulp. Water pre-hydrolysis was done at 150 °C for 90 min. The amount of lignin, xylan and glucan in the extracted pre-hydrolysis liquor (PHL) was 1.6, 4.9 and 1.6%, respectively. Pulping of pre-extracted chips was done following soda-AQ, alkaline sulfite and kraft process. The ratio of chip to liquor was 1:7 for both pre-hydrolysis and pulping. The kraft pulping process with 20% active alkali and 25% sulfidity at 150 °C for 90 min showed the best result. The lowest kappa number was 26.2 with a considerable pulp yield of 32.7%. The pulp was bleached by acidic NaClO2 and the consistency was 10% based on air-dried pulp. The lowest amount of 7% NaClO2 was used for the bleaching sequence of D0ED1ED2. After D0ED1ED2 bleaching, the pulp showed that α-cellulose, brightness and ash were 91.9, 77.9 and 1.6% respectively. The viscosity was 19.9 cP. Hence, there is a possibility to use banana plant stem as a raw material for dissolving grade pulp and other bioproducts.

Wood shortages, environmental pollution and high energy consumption remain major obstacles hindering the development of today’s pulp and paper industry. Energy-saving and environmental friendly pulping processes are still needed, especially for non-woody materials. In this study, soda-oxygen pulping of bagasse was investigated and a successful soda-oxygen pulping process for bagasse at 100 °C was established. The pulping parameters of choice were under active alkali charge of 23%, maximum cooking temperature 100 °C, time hold at maximum temperature 180 min, initial pressure of oxygen 0.6 MPa, MgSO4 charge 0.5%, and de-pithed bagasse consistency 12%. Properties of the resultant pulp were screened yield 60.9%, Kappa number 14, viscosity 766 dm3/kg, and brightness 63.7% ISO. Similar pulps were also obtained at 110 °C or 105 °C with a cooking time of 90 min. Compared with pulps obtained at higher temperatures (115–125 °C), this pulp had higher screened yield, brightness, and acceptable viscosity, while the delignification degree was moderate. These results indicated that soda-oxygen pulping at 100 °C, the lowest cooking temperature reported so far for soda-oxygen pulping, is a suitable process for making chemical pulp from bagasse. Pulping at lower temperature and using oxygen make it an environmental friendly and energy-saving pulping process.

Paper-based microfluidic devices (μPADs) are capable of achieving rapid quantitative measurements of a variety of analytes inexpensively. μPADs rely on patterning hydrophilic-hydrophobic regions on a sheet of paper in order to create capillary channels within impermeable fluidic brakes on the paper. Here, we present a novel, highly flexible and low-cost fabrication method using a desktop digital craft plotter/cutter and technical drawing pens with tip size of 0.5 mm. The pens were used with either commercial black permanent ink for drawing fluidic brakes, or with specialty in-house formulated aqueous inks. With the permanent marker ink it was possible to create barriers on paper rapidly and in a variety of designs in a highly flexible manner. For instance, a design featuring eight reservoirs can be produced within 10 s for each μPAD with a consistent line width of brakes (%RSD

Cationic nanofibrillar cellulose (C-NFC) has been prepared via a high pressure homogenization using quaternized cellulose fibers with glycidyltrimethylammonium chloride. It has been shown that the quaternization of dried softwood pulp facilitated the defibrillation processes and prevented clogging of the homogenizer. The effects of the trimethylammonium chloride content on the fibrillation yield, the transparency degree of the gel, the rheological behavior of the NFC suspension and their electrokinetic properties were investigated. AFM observation showed that the NFC suspension consisted of individualized cellulose I nanofibrils 4-5nm in width and length in the micronic scale. In addition to their strong reinforcing potential, the inclusion of C-NFC into a polymer matrix was shown to efficiently enhance the antibacterial activity. The reinforcing potential of C-NFC, studied by dynamic mechanical analysis (DMA), was compared to anionic NFC and the difference was explained in terms of the nanofibrils capacities to build up a strong networks held by hydrogen bonding.

A simple and low-cost fabrication method for paper-based diagnostic devices (PBDDs) is described in this study. Street-available polymer solutions were screen printed onto filter papers to create hydrophobic patterns for fluidic channels. In order to obtain fully functional hydrophobic patterns for fluids, the original polymer solutions were diluted with butyl acetate to yield a suitable viscosity range between 30-200 cP for complete patterning on paper. Typical pH and glucose tests with color indicators were performed on the screen printed PBDDs. Images of the PBDDs were analyzed by computers to obtain calibration curves for pH between 2 and 12 and glucose concentration ranging from 10-1000 mmol dm(-3). Detection of formaldehyde in acetone was also carried out to show the possibility of using this PBBD for analytical detection with organic solvents. An exemplar PBDD with simultaneous pH and glucose detection was also used to demonstrate the feasibility of applying this technique for realistic diagnostic applications.

In this work, polyelectrolyte complexes (PECs) were formed by adding polyacrylic acid (PAA) or 4-O-methylglucuronoxylan (Xyl) on poly(allylamine hydrochloride) (PAH) solutions, at different ionic strength and neutral pH. Turbidity curves, charge densities of the cationic complexes determined by polyelectrolyte titration method, and z-potential values showed clear differences between both complexes. Stirring favourably reverses the effects of sedimentation of Xyl/PAH complexes, as demonstrated by colloidal stability tests. Adsorption studies on silica surfaces, performed by Quartz Crystal Microbalance with Dissipation (QCM-D) showed that PAA/PAH adsorbed complexes layers were rigid, while the corresponding Xyl/PAH layers were viscoelastic. Despite the different conformations, both complexes were adsorbed as spherical particles, as observed by Atomic Force Microscopy (AFM). Adsorption isotherms performed on fibre suspensions showed that the ionic strength of the liquid medium determines the amount of PEC retained. Finally, it was found that the papermaking properties were significantly increased due to the addition of these PECs. Fil: Mocchiutti, Paulina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Instituto de Tecnología Celulosica; Argentina Fil: Galván, María Verónica. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Instituto de Tecnología Celulosica; Argentina Fil: Peresin, María S.. Technical Research Center Of Finland; Finlandia Fil: Schnell, Carla Natali. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Instituto de Tecnología Celulosica; Argentina Fil: Zanuttini, Miguel Angel Mario. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Instituto de Tecnología Celulosica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina

The influence of temperature (150–170 °C), pulping time (15–45 min) and soda concentration (5–10%) in the pulping of abaca on the yield, kappa, viscosity, breaking length, stretch and tear index of pulp and paper sheets, was studied. Using a factorial design to identify the optimum operating conditions, equations relating the dependent variables to the operational variables of the pulping process were derived that reproduced the former with errors lower than 25%. Using a high temperature, and a medium time and soda concentration, led to pulp that was difficult to bleach (kappa 28.34) but provided acceptable strength-related properties (breaking length 4728 m; stretch 4.76%; tear index 18.25 mN m2/g), with good yield (77.33%) and potential savings on capital equipment costs. Obtaining pulp amenable to bleaching would entail using more drastic conditions than those employed in this work.

Theoretical and experimental study of the paper drying process are presented. A mathematical model developed for combined heat ad mass transfer analysis of paper drying is given for both impinging air jets and through air drying methods. In this model, it is simply assumed that during the drying period of the paper has porous media and on the drying surface the vapour pressure of the evaporating liquid remains at a quasi-saturated value corresponding to the temperature of the liquid. The calculated transient paper temperatures in both methods agree well with the experimental results.

Cellulase treatment for decreasing viscosity and increasing Fock reactivity of dissolving pulp is a promising approach to reduce the use of toxic chemicals, such as hypochlorite in the dissolving pulp manufacturing process in the industry. Improving the cellulase treatment efficiency during the process is of practical interest. In the present study, the concept of using cationic polyacrylamide (CPAM) to enhance the cellulase treatment efficiency was demonstrated. This was mainly attributed to the increased cellulase adsorption onto cellulose fibers based on the patching/bridging mechanism. Results showed that the cellulase adsorption was increased by about 20% with the addition of 250 ppm of CPAM under the same conditions as those of the control. It was found that the viscosity decrease and Fock reactivity increase for the cellulase treatment was enhanced from using CPAM. The CPAM-assisted cellulase treatment concept may provide a practical alternative to the present hypochlorite-based technology for viscosity control in the industry.

Bacterial cellulose (BC) synthesized by Gluconacetobacter sucrofermentans CECT 7291 seems to be a good option for the restoration of degraded paper. In this work BC layers are cultivated and purified by two different methods an alkaline treatment when the culture media contains ethanol and a thermal treatment if the media is free from ethanol. The main goal of these tests was the characterization of BC layers measured in terms of tear and burst indexes, optical properties, SEM, X-ray diffraction, FTIR, degree of polymerization, static and dynamic contact angles, and mercury intrusion porosimetry. The BC layers were also evaluated in the same terms after an aging treatment. Results showed that BC has got high crystallinity index, low internal porosity, good mechanical properties and high stability over time, especially when purified by the alkaline treatment. These features make BC an adequate candidate for degraded paper reinforcement. © 2014 Elsevier Ltd.

The effectiveness of a biorefinery based on an HWE–Kraft–ECF bleaching process and the end use of pulp was systematically evaluated. Using a P-factor of 198, nearly 30% of xylan-based sugars were recovered. The resulting pulp and paper properties were found to be comparable with the control. A maximum xylan-based sugar recovery of nearly 50% was achieved at a P-factor of 738. Although the strength of this P-factor induced handsheet was lower than that of the control by about 20%, the corresponding pulp was sufficient for dissolving pulp application. However, once the P-factor rose above 1189, hemicellulose sugars were significantly degraded into furans; pulp and paper properties were also deteriorated due to cellulose degradation, lignin deposition and condensation. Thus, considering the different end use of pulps, the performance of an HWE-based biorefinery could be balanced by its HWE severity.

An enzymatic biobleaching sequence (L VA QPO) using a laccase from Trametes villosa in combination with violuric acid (VA) and then followed by a pressurized hydrogen peroxide treatment (PO) was developed and found to give high bleaching properties and meet dissolving pulp requirements: high brightness, low content of hemicellulose, satisfactory pulp reactivity, no significant cellulose degradation manifested by α-cellulose and HPLC, and brightness stability against moist heat ageing. The incorporation of a laccase–mediator system (LMS) to bleach sulphite pulps can be a good alternative to traditional bleaching processes since thermogravimetric analysis (TGA) showed that the laccase treatment prevented the adverse effect of hydrogen peroxide on fibre surface as observed during a conventional hydrogen peroxide bleaching treatment (PO). Although VA exhibited the best results in terms of bleaching properties, the performance of natural mediators, such as p -coumaric acid and syringaldehyde, was discussed in relation to changes in cellulose surface detected by TGA.

Paper-based devices provide an alternative technology for simple, low-cost, portable, and disposable diagnostic tools for many applications, including clinical diagnosis, food quality control, and environmental monitoring. In this study we report a two-step fabrication process for creating two-dimensional microfluidic channels to move liquids on a hydrophobized paper surface. A highly hydrophobic surface was created on paper by TiO2 nanoparticle coating using a high-speed, roll-to-roll liquid flame spray technique. The hydrophilic pattern was then generated by UV irradiation through a photomask utilizing the photocatalytic property of TiO2. The flow dynamics of five model liquids with differing surface tensions 48-72 mN·m(-1) and viscosities 1-15 mN·m(-2) was studied. The results show that the liquid front (l) in a channel advances in time (t) according to the power law l=Zt0.5 (Z is an empirical constant which depend on the liquid properties and channel dimensions). The flow dynamics of the liquids with low viscosity show a dependence on the channel width and the droplet volume, while the flow of liquids with high viscosity is mainly controlled by the viscous forces.

The main objective of this study was to analyse cost reduction by reducing the use of fresh water in the cellulose bleaching process and to make it easier to obtain water in a closed circuit. Eucalyptus oxygen delignified industrial pulp was used. The pulp was bleached 10 times in the D(E+P)DP sequence in the same conditions. Counter current washing was used in the bleaching stages, and each sequence was carried out with different wash factors: 9, 6, 3, and 0 m³ of distilled water/ton of oven dry pulp. The goal was to reach brightness of 92±0.5% ISO. The results showed that there was a chemical oxygen demand (COD) increase and brightness reversion, but the kappa number and viscosity did not change. The apparent colour was increased by increasing COD in the effluent during the cycles and by decreasing the wash water. Up to 3 m³/t of water was tolerable and even recommended to wash pulp. Nine cubic metre per tonne of fresh water is most commonly used in the industry, so water savings make the implementation of the process possible.